tailored polymers through rational monomer development...q3 fy19 : synthesize and characterize at...
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Managed by Triad National Security, LLC for the U.S. Department of Energy’s NNSA
Tailored Polymers Through Rational
Monomer Development
PI: Andrew D Sutton
March 4th, 2019
Technology Session Review Area:
Performance-Advantaged Bioproducts and
Separations Consortium
Goal Statement
3/19/2019 | 2Los Alamos National Laboratory
Goal: Develop polymers that provide a performance advantage over current
petroleum based polymers and incorporate a readily accessible degradation
pathway
– Performance advantages include thermal stability, processability, cost, and primarily biodegradability
– Valorize by-products of biofuel production, e.g. glycerol, acetoin
– Develop a degradation route in order to avoid long-term environmental accumulation problems
Outcome: Multiple new bio-derived polymers using the highly versatile acetal
monomer platform
– Identify petroleum based competitors where these polymers can offer a performance advantage
– Adaptable functionality to address multiple applications and polymer synthesis pathways
– Bio-derived materials with improved environmental impact at end-of-life
Relevance: Advance bioeconomy by providing performance advantaged materials
– Eliminates the need to charge a “Green Premium” through economical pathways
– Production of materials with no long-term environmental impact
– Byproduct valorization reduces production costs of bio-renewable products
Quad Chart Overview
3/19/2019 | 3Los Alamos National Laboratory
Timeline
– Start Date: October 2018
– End Date: September 2020
– Percent Complete: 25 %
End of Project GoalSynthesize, characterize and test > 1 new bio-derived
polymer that offers improved thermal and physical
properties over petrochemical polymers with the additional
ability to degrade readily to the monomer precursors under
certain conditions. Perform initial TEA on these materials in
order to present a cost and performance based value-
proposition for further work or commercialization.
Objective
Synthesis of performance advantaged polymers
from small, readily available bio-derived molecules
to valorize byproducts of biofuel production.
Total
Costs
Pre FY17
FY17
Costs
FY18
Costs
Total
Planned
Funding
(FY19-
Project
End
Date)
DOE
funded-- -- $0k $550k
Partners:
BETO Projects: Inverse Biopolymer Design through
Machine Learning and Molecular Simulation, Performance
Advantaged Bioproducts from Catalytic Fast Pyrolysis,
Analysis in support of novel bio-based products and
functional replacements
Nat’l labs, universities, companies: National Renewable
Energy Lab (NREL)
• Ct-J Identification and Evaluation of Potential Co-products– Using bioderived building blocks to synthesis novel monomers
• Ct-K Developing methods for co-product production– Developing pathways to novel polymeric materials using simple bio-derived
molecules.
Barriers addressed
Project Overview
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History: Dioxolane synthesis for fuel applications
inspired potential chemical applications
• Focus: Use simple bio-derived building blocks to construct
tunable monomers through defunctionalized/derivatized
functional groups
• Leverage catalysis expertise developed within the BETO
portfolio
• Expands work developed on acetalization for fuels use1,2.
Context: Develop polymers which can degrade to
benign starting materials
• Develop polymers with improved performance and no
long-term environmental accumulation problems
• Use the performance advantages to avoid a “Green
Premium”
Project Goals:
– Develop a range of monomers comprised of benign
building blocks that can be selectively
defunctionalized/derivatized
– Produce polymers and test for performance advantaged
properties
– Identify stimuli that can decompose polymers to
monomers and the original building blocks
1Moore et al, Green Chem., 2017, 19, 169 2Staples et al, Sustainable Energy Fuels, 2018, 2, 2742.
EtOH- H2
O
H
O
H
O
H
O
Amberlyst 15, Pd/C
Ar/H2 (94/6, 200 psi)cyclohexane1. 60 oC, 1h2. 100 oC, 3h
> 95 % Isolated
Yield
Amberlyst 15
RT, 3h
> 95 % isolated
Yield
O
O
O
O
O
O
H
OH
2-ethylhexanalCommodity Chemical
DCN = 45
DCN = 46
DCN = 49
DCN = 33
DCN = 45
DCN = 64
Ni-SiO2/Al2O3H2 200 psi, 3h
O
O
O
O
O
O
DCN = 86
DCN = 94
DCN = 124
EtOHAmberlyst 15
RT, 3h
> 95 % isolated
Yield
Alcohols
HZSM-5, Pd/CH2, 100 psi
100 oC, 5 min
Alkanes
Market of > 3M tons/yearCurrent market cost $1700/tonCAGR 3-5% for the next 5 yearsPrelim TEA ~ $500/ton
BDO
Management Approach
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• Team Structure
– Andrew Sutton (PI)
– Cameron Moore (Co-PI)
– Chris Roland (PD)
– Gregg Beckham (NREL)
• Material characterization and performance
– Mike Crowley (NREL)
• Machine learning for improved polymer
development
• Consortium Interfacing
– Monthly conference call with PABP and BETO
technology manager
– Discussions with other PABP projects as
interests converge
• Industry Engagement
– Customer discovery interviews underway (Q2
Milestone)
Selected Project Milestones
Q3 FY19 : Synthesize and characterize at
least 3 monomers from bioderived building
blocks. Measure physical properties and
hydrolytic stability.
Q4 FY19 : Perform polymerization on at
least 5 monomers and perform initial
characterization/testing of these materials.
End of Project : Synthesize, characterize
and test > 1 new bio-derived polymer that
offers improved thermal and physical
properties over petrochemical polymers with
the additional ability to degrade readily to the
monomer precursors under certain
conditions.
Technical Approach
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Hypothesis: Can we construct polymers from environmentally benign building blocks
that can be degraded by a stimulus to give the original, benign starting materials?
Small BioderivedBuilding Blocks
Monomers
Polymers
Decomposition Polymerization
Synthesis
This gives the opportunity to develop monomers that can provide a pathway for safe
plastic degradation/recycle upon reaching end-of-life to avoid plastic accumulation
Technical Approach
3/19/2019 | 7Los Alamos National Laboratory
Glycerol and acetone known to give solketal which is prone to hydrolysis
Would subtle modification increase thermal stability and increase synthetic utility?
Decomposition of
dioxolanes at 80 C.
Demonstrates that subtle structural and therefore electronic changes in the molecule can change the physical
properties. Does this provide an opportunity to tune monomers and influence polymer performance?
Technical Approach
3/19/2019 | 8Los Alamos National Laboratory
• Acetal/Ketal functionality can be
incorporated into polymer
backbone using monomers made
from bio-derived small molecules
• 2 million metric tons/year of
glycerol produced as a byproduct
of biodiesel production
• Large effect of small structural
changes on monomer properties
has been previously
demonstrated
• Incorporation of functional groups
allows for extensive derivatization
or defunctionalization and
alternative polymerization
approaches
Technical Approach
3/19/2019 | 9Los Alamos National Laboratory
• Potential polycarbonate applications:
– Polycarbonates are commonly used for their combination of impact strength, optical clarity, heat
resistance, favorable processability and in lightweight applications such as vehicle composites
– 5100 Kt/year global polycarbonate production capacity in 2016
– Global market valued at $13,000,000,000 in 2016, expected to grow to $17,000,000,000 by 2020
• Polycarbonates are commonly synthesized via base-catalyzed reaction between diols
and carbonates
• By using bio-derived pH responsive diols, stimuli response can be incorporated into
polymer backbone
Plastics Insights, Polycarbonate Production, Price and Market Demand
Technical Approach
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Highly versatile monomers can be functionalized to
be suitable for conventional alkyne polymerization
Combination of condensation and vinyl polymerization
can be combined to make graft copolymers
Functional groups can be derivatized through
reactions such as aminations to increase chain-chain
H-bonding
Using tri or multifunctional monomers in blend will
introduce cross-linking, improving physical
properties
Laboratory Capabilities
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• Lab equipped with DSC, GC-MS/FID/PolyArc, NMR,
TGA, HPLC, and GPC
• All polymer and small molecule characterization
can be done in-house
• New Infinity II GPC equipped with triple detection –
viscometer, RI and Light Scattering
• Particle size, intermolecular interactions and
polymer topology
• Material properties will be measured in collaboration with
NREL (Beckham)
Technical Accomplishments
3/19/2019 | 12Los Alamos National Laboratory
• Aggregation of physical and material
properties of commercial polycarbonates
• Synthesis of pH responsive monomer
from bio-derived small molecules
• Biorenewable polymers from bio-derived
monomers
• Depolymerization of biorenewable
polymers
• Bio-derived Monomer design
optimization
Environmentally Benign
Bio-derived Small
Molecules
pH Responsive Bio-
derived Monomer
Monomer Synthesis
pH Responsive
Polycarbonate
Baseline Performance Property Report
3/19/2019 | 13Los Alamos National Laboratory
• Goal: Establish baseline set of material properties bioproducts must meet in order to compete
with petroleum based materials
• Properties pulled from Technical Data sheets for 25+ commercial polycarbonates
Commercial Aliphatic Polycarbonates
Tg range -10°C - 40°C
Tensile Strength 300 – 600 PSI
Commercial Aromatic Polycarbonates
Tg range 110°C - 230°C
Tensile Strength 8500 – 10500 PSI
• Lessons Learned: Aliphatic polycarbonates more niche uses, smaller market share and inferior
mechanical properties, while aromatic polycarbonates possess more robust mechanical and
thermal properties, and are a larger share of commercial polycarbonate market
Bio-derived Monomer Synthesis
3/19/2019 | 14Los Alamos National Laboratory
• Standard acetalization yield is currently low
– Direct synthetic method is being refined
• Model monomer synthesis can be achieved using
protected starting materials
• Monomer isolated in high yield ( ~ 90 %) and high
purity as mixture of several isomers.
• Two monomers synthesized and characterized
• Solketal model monomer compound gives mixed
primary/secondary alcohols
• Gycerol with hydroxyacetone gives dual primary
monomer
BnO
OH
OH
O
OAc
BnO
OO
OAc
p-TsOH·H2O
BnO
OO
OAc
K2CO3 MeOH
Pd/C, H2 EtOH
OH
OO
OH
BnO
OH
OH OH
O BnO
OO
OHp-TsOH·H2O
BnO
OO
OH
K2CO3 MeOH
Pd/C, H2 EtOH
OH
OO
OH
Polymerization/Degradation
3/19/2019 | 15Los Alamos National Laboratory
• Preliminary Results: Depolymerization appears successful to carbonate linked unit• 10 mg of poly(solketal carbonate) in 2mL of aqueous hydrochloric acid (0.5 – 12M), solubility
increases with acidity
• GPC indicates one species and no polymer remaining
• Structure confirmed by GC-MS and NMR
• Intentionally limited n (3:1 monomer to carbonate ratio) to derive a small oligomer for degradation
studies (Average Mn ~ 5200, D = 1.75)
• Initial physical properties, including glass transition temperature are similar/superior to commercial
aliphatic carbonates – should improve when n is not constrained
Polymerization
Relevance and Impact to BETO
3/19/2019 | 16Los Alamos National Laboratory
Goal: Develop polymers that provide a performance advantage over current petroleum
based polymers and incorporate a readily accessible degradation pathway
Why is this project important and what is the relevance to BETO and bioenergy goals?
- A polymer with improved properties vs. a direct replacement has the potential for rapid market entry
- Co-products can enable the production of biofuels and therefore stimulate the bio-economy due to
higher selling price
- Utilization of small commonly produced by-products and bio-derived molecules will increase overall
carbon yield of biomass processes.
- Support of BETO milestone: By 2025 produce bioproducts at needed scales (20-100kg) for
product testing to support off-take agreements and end-user/market acceptance
- Increase Yield from Catalytic Processes. Identifying catalyst and process conditions to
increase overall reaction yield, minimize carbon loss and decrease the formation of undesirable
intermediates (Ct-F).
- Identify and Evaluate Potential Bioproducts. Conversion processes need to integrate
bioproduct production with that of drop-in fuels. Link intermediates from specific processes with
potential products. Novel molecules also require high-throughput screening to characterize and
optimize them for properties that are advantageous to the molecules already used in industrial
processes (Ct-J).
- Develop Methods for Bioproduct Production. Properties present in molecules tested at the lab
and bench scale must be understood fundamentally to enable a transfer to larger scales (Ct-K).
Relevance and Impact to Advance State of Technology
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Goal: Develop polymers that provide a performance advantage over current petroleum
based polymers and incorporate a readily accessible degradation pathway
How does this project advance the State of Technology and contribute to commercial viability of
biofuels production?
- Using versatile monomers where functional groups can be readily altered will help guide rational design
of monomers based on structure-function relationships and guided my machine learning and molecular
modelling
- Production of bioproducts is essential to enable biofuel production and therefore the bioeconomy
Technology transfer activities
- Customer discovery interviews underway based on previous Energy I-Corp participation
- Results will be published in peer reviewed journals
- LANL invention disclosures have been filed
Future Work
3/19/2019 | 18Los Alamos National Laboratory
• Expand monomer scope – incorporation of different bio-derived linkers to tune physical
properties e.g. cross-linking, H-bonding
• Optimize polymer synthetic conditions for increased yield and pH response/hydrolytic
stability
• Increase polymer yields and fully characterize the physical and material properties
• Incorporate milder stimuli for polymer decomposition
• Explore alternative polymerization approaches
• Work closely with Inverse Polymer Design to develop iterative design cycles
– Demonstrate at least one cycle of iteration with predictive modelling to improve
monomer/polymer properties (Milestone Q4 FY19)
– Feedback from NREL will direct research towards ideal monomer properties
• Full materials characterization on most promising polymers (collaboration with
NREL)
Summary
3/19/2019 | 19Los Alamos National Laboratory
Overview– Develop polymers that can readily degrade to benign molecules while providing a performance
advantage over current petroleum based polymers
Approach– Use current expertise in acetal formation to synthesize monomers that can be converted to the
parent building blocks and capitalize on the abundant functional groups to allow for structural and electronic optimization in collaboration with computational approaches
Technical accomplishments– Increased stability of monomers
– Multiple monomers have been synthesized and characterized
– Polymerization and degradation of the polymers has been performed
Relevance– Provides a polymer with a designed degradation route in order to avoid long-term environmental
accumulation problems
– Give pathway for lesser used bioproducts (i.e. glycerol) to be reintroduced to the bioeconomy and increases global carbon efficiency
– By making a better product we can accelerate commercialization
Future work– Increase polymer yields and fully characterize the physical and material properties
– Develop milder stimuli for polymer decomposition
– Expand substrate scope to introduce additional functionality
– Explore alternative polymerization approaches
– Work closely with Inverse Polymer Design to develop iterative design cycles
Acknowledgments
3/19/2019 | 20Los Alamos National Laboratory
BETO
Nichole Fitzgerald
Jessica Philips
Contributors (LANL)
Cameron Moore
Chris Roland
Orion Staples
PABP Collaborators (NREL)
Gregg Beckham
Performance Advantaged Bioproducts via Selective Biological and Catalytic Conversion
Mary Biddy
Analysis in Support of Novel Bio-based Products and Functional Replacements
Mike Crowley
Inverse Biopolymer Design Through Machine Learning and Molecular Simulation
Mark Nimlos
Performance Advantaged Bioproducts from Catalytic Fast Pyrolysis
Polycarbonate Physical Property Data
3/19/2019 | 21Los Alamos National Laboratory
Polymer
Trade
Name
Chemical
Formula
Molecular
Weight Range Density RI Tg Tm
Thermal
Conductivity
(J/molK)
Entanglement
Molecular Weight Technical Data Sheet
Poly(ethylene
carbonate) QPAC 25 (C3H4O3)n 50k-200k 1.42 1.47 0-10 C NR NR NRhttp://empowermaterials.com/wp-content/uploads/2014/11/QPAC-25-Technical-
Data-Sheet.pdf
Poly(propylene
carbonate) QPAC 40 (C4H6O3)n 100k-300k 1.26 1.463 15-40C NR NR NRhttp://empowermaterials.com/wp-content/uploads/2014/11/QPAC-40-Technical-
Data-Sheet.pdf
Polyco(proplyene
cyclohexene
carbonate)
QPAC
100 (C11H16O6)n 150k-200k 1.04 NR 90-100C NR NR NRhttp://empowermaterials.com/wp-content/uploads/2014/11/QPAC-100-Technical-
Data-Sheet.pdf
Poly(Cyclohexene
carbonate)
QPAC
130 (C7H10O3)n 150k-200k 1.1 NR
120-
130C NR NR NRhttp://empowermaterials.com/wp-content/uploads/2014/11/QPAC-130-Technical-
Data-Sheet.pdf
Poly(butylene
carbonate) QPAC 60 (C5H8O3)n NR NR NR 0-20C NR NR NRhttp://empowermaterials.com/wp-content/uploads/2017/11/QPAC-60-Safety-
Data-Sheet.pdf
Poly(pentene
carbonate) (C6H10O3)n 8k-50k NR NR -4C NR NR NR https://onlinelibrary.wiley.com/doi/10.1002/app.12355
Poly(Hexene
Carboante (C7H12O3)n 10k-50k NR NR -10C NR NR NR https://onlinelibrary.wiley.com/doi/10.1002/app.12355
Poly(Bisphenol A
Carbonate)
Lexan/Ma
krolon (C16H15O3)n NR 1.2 1.53-1.59
147-
174C NR 305 1700-4800 https://polymerdatabase.com/polymers/polybisphenolacarbonate.html
Poly(Bisphenol B
Carbonate) Same (C17H17O3)n NR 1.18 1.58
134-
149C NR NR (Calc 321-337) NR (Calc 2700-2800) https://polymerdatabase.com/polymers/polybisphenolbcarbonate.html
Poly(Bisphenol F
Carbonate) Same (C14H11O3)n NR 1.24
NR (Calc
1.49-1.64)
120-
147C NR NR (Calc 249-267) NR (Calc 2350-2450) https://polymerdatabase.com/polymers/polybisphenolfcarbonate.html
Poly(2,6,3',5'-
tetrachloro bisphenol
A Carbonate) Same
(C16H11O3Cl
4)n NR
NR (Calc
0.89-0.95) 1.59-1.61
220-
230C NR NR (Calc 360-390) NR (Calc 2500-5700)https://polymerdatabase.com/polymers/Poly2635-
tetrachlorobisphenolAcarbonate.html
Poly(tetramethyl
bisphenol A
carbonate) Same (C20H23O3)n NR 1.08
NR (Calc
1.49-1.53) 194C NR
NR (Calc 389.6-
420.7) 3230-3620 https://polymerdatabase.com/polymers/polytetramethylbisphenolacarbonate.html
Poly(4,4'-
thiodephenylene
carbonate) Same (C13H9O3S)n NR 1.36
NR (Calc
1.63-1.69)
110-
115C NR NR (Calc 255-262) NR (Calc 2500-2750) https://polymerdatabase.com/polymers/poly44-thiodiphenylenecarbonate.html
Physical Properties by repeat unit
Polycarbonate Physical Property Data
3/19/2019 | 22Los Alamos National Laboratory
Company Resin Product # Density Tensile Strength (PSI) Glass Transition RI Thermal Conductivity (BTUin/hrft^2F)
Lubrizol Carbothane TPU Aliphatic PC-3575A 1.15 600 -29 NR NR
PC-3585A 1.15 425 -27 NR NR
PC-3595A 1.15 400 -25 NR NR
PC-3555D 1.15 325 -25 NR NR
PC-3572D 1.15 325 NR NR NR
Carbothane TPU Aromatic AC-4075A 1.19 400 -23 NR NR
AC-4085A 1.2 400 -24 NR NR
AC-4095A 1.21 370 -10 NR NR
AC-4055D 1.22 300 NR NR NR
Aetna Makrolon GP 1.2 9500 NR 1.586 1.35
GP-V 1.2 9500 NR 1.586 1.35
AR 1.2 9500 NR 1.586 1.35
MG 1.2 9500 NR 1.586 1.35
FI 1.2 9500 NR NR NR
SABIC LEXAN 123X 1.2 61625 NR NR NR
4251R 1.2 58000 NR NR NR
4501 1.2 47125 NR NR NR
943X 1.2 47125 NR NR NR
ADX1016R 1.2 58000 NR NR NR
Empower
Materials QPAC 25 1.42 NR 0-10C 1.47 NR
40 1.26 NR 15-40C 1.26 NR
100 1.04 NR 90-100C NR NR
130 1.1 NR 120-130C NR NR
Plaskolite
(Covestro) Tuffak GP 1.2 9500 NR 1.586 1.35
M5 1.2 9500 NR NR NR
LD 1.2 9500 NR NR 1.35
DSM
Engineering Xantar 17 1.01 8700 NR NR 1.67
C CF 107 1.17 8700 NR NR NR
G2F 23 UR 1.25 9430 NR NR NR
Physical Properties by Trade Name
Biorenewable Polymers from bio-derived Monomers
3/19/2019 | 23Los Alamos National Laboratory
Outcome: Initial physical properties, including glass transition
temperature are similar/superior to commercial aliphatic
carbonates – should improve when n is not constrained
• Polycarbonates are used for medical plastics, heat resistance, transparent materials, etc.
• Performance Advantage: Maintain physical properties and selectively depolymerize
• Bio-Based monomer: Solketal derived from Glycerol and Acetoin
• Hypothesis: Intentionally limited n (3:1 monomer to carbonate ratio) in order to derive a
small discrete oligomer for degradation studies.
Polymer Tg (°C)
Poly(ethylene carbonate) 0-10
Poly(propylene carbonate) 15-40
Poly(butylene carbonate) 0-20
Poly(pentene carbonate) -4
Poly(hexene carbonate) -10
Poly(solketal carbonate) 10